Anti-wrinkle silicone polysaccharide compounds and compositions comprising said compounds

ABSTRACT

The present invention relates to compounds, and laundry compositions comprising said compounds, which are capable of providing enhanced anti-wrinkle benefits to cellulosic fiber containing fabric, said compounds having the formula: 
                 
 
wherein each R unit is independently a siloxane units having the formula: 
                 
 
wherein each R 2  is independently a C 1 -C 22  linear or branched, substituted or unsubstituted hydrocarbyl moiety; the index p is from 0 to about 50; L is a linking group; the index q is 0 or 1; R 1  units are fabric substantive units having the formula:
 
—[(CH 2 ) j (R 3 O) k ]R 4 
 
wherein R 3  is C 2 -C 12  linear or branched alkylene; R 4  is hydrogen, an anionic unit, and mixtures thereof; the index j is from 0 to about 25; the index k is from 0 to about 50; the sum of the indices x+y+z=n wherein n has an average value of from 5 to about 6000;.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Application Ser. No. 60/337,941, filed Dec. 7, 2001.

FIELD OF THE INVENTION

The present invention relates to polysaccharide oligomers and/orpolymers that are modified to provide compounds having an anti-wrinklebenefit to garments and textiles. The present invention further relatesto laundry detergent compositions that comprise said anti-wrinklebenefit compounds.

BACKGROUND OF THE INVENTION

Fabric, primarily cellulose comprising fabric, inter alia, cotton, has apropensity to wrinkle when laundered. Cotton fabric, which secondarystructure is determined by the hydrogen bonds formed between proximalsaccharide residues, becomes wrinkled when said hydrogen bonds areformed between units that are further away from one another than theoriginal bonds. Wrinkling can occur under a number of circumstancesincluding loss of nascent water from fabric while the fabric is notspread flat or if the fabric is mechanically bent or folded.

Manufacturers of cellulose comprising fabric have long sought to abatethe propensity of this type of fabric to wrinkle. One means has been totreat the fabric during the manufacture stage with crosslinking agentsthat provide a rigid fiber matrix, for example, permanent presstreatments involving formaldehyde or other reactive crosslinking agents.

Treatment of fabric, however, can relate to the loss of properties whichare desired, inter alia, strength, breathability, softness. There istherefore a long felt need for a means of providing anti-wrinklebenefits to fabric which does not modify the surface of the fabric in amanner which detracts from the fabric qualities.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned needs in that it has beensurprisingly discovered that polysaccharide oligomers and polymers thathave been modified with siloxane units and a anionic, nonionic, cationicor zwitterionic unit provides anti-wrinkle benefits.

The first aspect of the present invention relates to compounds which arecapable of providing enhanced anti-wrinkle benefits to cellulosic fibercontaining fabric, said compounds having the formula:

wherein each R units are independently siloxane units having theformula:

wherein each R² is independently a C₁-C₂₂ linear or branched,substituted or unsubstituted hydrocarbyl moiety; the index p is from 0to about 50; L is a linking group; the index q is 0 or 1; each R¹ unitis independently fabric substantive units having the formula:—[(CH₂)_(j)(R³O)_(k)]R⁴wherein R³ is C₂-C₁₂ linear or branched alkylene; R⁴ is hydrogen, ananionic unit, and mixtures thereof; the index j is from 0 to about 25;the index k is from 0 to about 50; the sum of the indices x+y+z=nwherein n has an average value of from 5 to about 6000.

The present invention further relates to laundry detergent compositionscomprising the anti-wrinkle compounds of the present invention.

Another aspect of the present invention relates to methods for providingenhanced anti-wrinkle benefits to fabric.

These and other objects, features, and advantages will become apparentto those of ordinary skill in the art from a reading of the followingdetailed description and the appended claims. All percentages, ratiosand proportions herein are by weight, unless otherwise specified.

All temperatures are in degrees Celsius (° C.) unless otherwisespecified. All documents cited are in relevant part, incorporated hereinby reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to modified polysaccharides that provideanti-wrinkle benefits to cellulosic fabric, especially cotton fabric.The compositions of the present invention that comprise said modifiedpolysaccharides are capable of enhancing the anti-wrinkle capacity ofclothing or other fabric comprising articles of manufacture.

It has now been surprisingly discovered that oligomeric and polymericpolysaccharides can be modified to provide anti-wrinkle benefits. Thefirst modification is the attachment of a siloxane comprising unit whichmodifies the surface of fabric to provide the anti-wrinkling benefit.The second modification is the attachment of an anionic, nonionic,cationic or zwitterionic unit to the polysaccharide which provides thefinal compound with increased water dispersibility or increased watersolubility depending upon the final molecular weight.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

Definitions

Herein “hydrocarbyl” means any unit which comprises carbon and hydrogenatoms, whether linear, branched, cyclic, acyclic, and regardless of howmany of the hydrogen atoms are substituted for with a suitablesubstituted unit as defined herein below. Non-limiting examples of“hydrocarbyl” units include methyl, benzyl, 6-hydroxyoctanyl,m-chlorophenyl, 2-(N-methylamino)propyl, and the like.

Herein “substituted” means replacement of a hydrogen atom, two hydrogenatoms, or three hydrogen atoms from a carbon atom to form a moiety, orthe replacement of hydrogen atoms from adjacent carbon atoms to form amoiety. For example, a substituted unit that requires a single hydrogenatom replacement includes halogen, hydroxyl, and the like. A twohydrogen atom replacement includes carbonyl, oximino, and the like.Three hydrogen replacement includes cyano, and the like. The termsubstituted is used throughout the present specification to indicatethat a moiety, inter alia, aromatic ring, alkyl chain, can have one ormore of the hydrogen atoms replaced by a substituent. For example,4-hydroxyphenyl is a “substituted aromatic carbocyclic ring”, and3-guanidinopropyl is a “substituted C₃ alkyl unit.”

The following are non-limiting examples of moieties, which can replacehydrogen atoms on carbon to form a “substituted hydrocarbyl” unit:

i) —NHCOR³⁰;

ii) —COR³⁰;

iii) —COOR³⁰;

iv) —COCH═CH₂;

v) —C(═NH)NH₂;

vi) —N(R³⁰)₂;

vii) —NHC₆H₅;

viii) ═CHC₆H₅;

ix) —CON(R³⁰)₂;

x) —CONHNH₂;

xi) —NHCN;

xii) —OCN;

xiii) —CN;

xiv) F, Cl, Br, I, and mixtures thereof;

xv) ═O;

xvi) —OR³⁰;

xvii) —NHCHO;

xviii) —OH;

xix) —NHN(R³⁰)₂;

xx) ═NR³⁰;

xxi) ═NOR³⁰;

xxii) —NHOR³⁰;

xxiii) —CNO;

xxiv) —NCS;

xxv) ═C(R³⁰)₂;

xxvi) —SO₃M;

xxvii) —OSO₃M;

xxviii) —SCN;

xxix) —P(O)H₂;

xxx) —PO₂;

xxxi) —P(O)(OH)₂;

xxxii) —SO₂NH₂;

xxxiii) —SO₂R³⁰;

xxxiv) —NO₂;

xxxv) trihalomethyl having the formula: —CF₃, —CCl₃, —CBr₃;

xxxvi) and mixtures thereof;

wherein R³⁰ is hydrogen, C₁-C₂₀ linear or branched alkyl, C₆-C₂₀ aryl,C₇-C₂₀ alkylenearyl, and mixtures thereof; M is hydrogen, or a saltforming cation.

Herein “polysaccharide” means any material comprising a saccharidehaving the formula described herein below containing the number of unitsas described herein below. The terms “oligosaccharide”,“polysaccharide”, “cellulose”, “cellulose polymers”, “cellulosepolysaccharides” and the like are used interchangeably throughout thepresent specification and are intended to stand for the materials whichare suitable backbones for the compounds of the present invention.

Anti-wrinkle Compounds

The anti-wrinkle fabric enhancing compounds of the present invention arepolysaccharide oligomers or polymers having the formula:

wherein the molecular weight of the polysaccharide prior to modificationis defined by the value of the index n which is the sum of theindividual units x+y+z. The polysaccharides of the present invention maycomprise any linkage; including x to y; x to z; and y to z or mixturesthereof. The above structure also only exemplifies saccharide linkageswhich are 1,4-linked, however, units having 1,3 links, for example, theformula:

wherein x+y+z=n, are also an aspect of the present invention, as well as1-6 linkages and mixtures of 1-3, 1-4, and 1-6 linked polysaccharides.

In addition, the residues may comprise acid groups, for example,glucuronic acid units having the formula:

Because any source of polysaccharide will comprise oligomers and/orpolymers of mixed length, the index n represents an average value exceptin the instances wherein the exact number of units can be determined.The index n has an average value of from about 5 to about 6000, however,one aspect of the present invention relates to polysaccharides having anaverage value of the index n from about 10 to about 3000. Another aspectof the present invention provides embodiments wherein n has an averagevalue of from about 15 to about 1000.

The polysaccharide compounds of the present invention are modified bythe substitution of X units that are hydrogen with X units that areeither R units or R¹ units. R units and R¹ units each provide separatefabric benefit enhancing properties. One aspect of the present inventionrelates to polysaccharide compounds wherein less than 50% of thepolysaccharide residues have at least one X unit that is hydrogenreplaced by a R or R¹ unit. Another aspect of the present inventionrelates to modified polysaccharide compounds wherein less than 25% ofthe residues have X units which are R or R¹ units, while still anotheraspect relates to compounds having less than 10% by weightmodifications. Other aspects or the present invention, as describedherein below, relate to the number of residues which are substituted byR or R¹ units, the ratio of R to R¹ units present, and the carbonposition onto which the substitution takes place (for example, C(2),C(3), or C(6) position).

R units are siloxane comprising units and serve to provide the finalcompound with a unit which modifies the surface of fabric therebyproviding anti-wrinkling benefits. Each R unit independently has theformula:

wherein each R² is independently a C₁-C₂₂ linear or branched,substituted or unsubstituted hydrocarbyl moiety; an alkyleneamino unithaving the formula —CH₂)_(m)N(R⁷)₂ wherein R⁷ is hydrogen, C₁-C₁₂ linearor branched, substituted or unsubstituted hydrocarbyl moiety. The lengthof the silicone containing unit is defined by the index y which itselfis also an average value. For example, a discrete mixture of R unitshaving a 50:50 mixture of chains having respectively 7 siliconecontaining units and 8 silicone containing units will have an average pvalue of about 6.5. The index p can have an average value of from 0,wherein only an (R²)₃Si— unit is present, to about 50. One aspect of thepresent invention relates to R units wherein the index p is from 0 toabout 20, however, another embodiment comprises R units wherein theindex p is from 0 to about 10.

One embodiment of the present invention comprises R units that are amixture of siloxane units comprising phenyl, C₁-C₁₈ alkyl, or mixturesthereof. Another aspect of the present invention relates to R unitswherein each R² is independently C₁-C₁₂ alkyl, and mixtures thereof. Inone embodiment of this each aspect R² is independently C₁-C₆ alkyl. Oneembodiment of the present invention comprises R units that entirelycomprise R² units which are methyl.

R units can be directly attached to the polysaccharide backbone, howevermany aspects of the present invention require the use of a linking unit,L, to facilitate attachment of the siloxane unit to the oligomer orpolymer backbone. When a linking unit is present the index q is equal to1 whereas, when L is absent, q is equal to 0. Any unit that allowsattachment of an R unit to the backbone is suitable for use in thepresent invention, however, one aspect of the present invention utilizesL units independently selected from the group consisting of:

i) —[C(R⁵)₂]_(d)—; wherein d is from 1 to 30;

ii) —[C(R⁵)₂]_(d)(CH═CH)_(d′)—; wherein d is from 0 to 30; d′ is from 1to 30;

iii) —C(X)—;

iv) —OC(X)—;

v) —C(X)O—;

vi) —[C(R⁵)₂]_(e)C(X)X(R⁶O)_(d)—; wherein d is from 0 to 30; e is from 1to 30;

vii) —(OR⁶)_(j)XC(X)[C(R⁵)₂]_(e)—; wherein d is from 0 to 30; e is from1 to 30;

viii) —[C(R⁵)₂]_(e)C(X)(R⁶O)_(j)—; wherein d is from 0 to 30; e is from1 to 30;

ix) —(OR⁶)_(d)C(X)[C(R⁵)₂]_(e)—; wherein d is from 0 to 30; e is from 1to 30;

x) —C(X)NR⁵—;

xi) —C(X)R⁶C(X)—;

xii) —C(X)NR⁵C(X)—;

xiii) —C(X)NR⁵R⁶NR⁵C(X)—;

xiv) —NR⁵C(X)—;

xv) —NR⁵C(X)NR⁵—;

xvi) —NR⁵C(X)R⁶NR⁵—;

xvii) —NR⁵R⁶C(X)NR⁵—;

xviii) —NR⁵C(X)R⁶C(X)O—;

xix) —OC(X)R⁶C(X)NR⁵—;

xx) —NR⁵C(X)R⁶C(X)O—;

xxi) —NR⁵C(X)NR⁵R⁶—;

xxii) —R⁶NR⁵C(X)NR⁵—;

xxiii) —NR⁵C(X)NR⁵R⁶—;

xxiv) —R⁶NR⁵C(X)NR⁵R⁶—;

xxv) —NR⁵—;

xxvi) —R⁶NR⁵—;

xxvii) —NR⁵R⁶—;

xxviii) —NR⁵N═N—;

xxix) —NR⁵NR⁵—

xxx) —OR⁶—;

xxxi) —R⁶O—;

xxxii) —R⁶OR⁶—;

xxxiii) —(R⁶)_(u)C(X)(R⁶)_(u)—;

xxxiv) —(R⁶)_(u)OC(O)(R⁶)_(u)—;

xxxv) —(R⁶)_(u)C(O)O(R⁶)_(u)—;

xxxvi) —(R⁶)_(u)OC(O)O(R⁶)_(u)—;

wherein R⁵ is hydrogen, C₁-C₂₂ linear or branched alkyl, C₁-C₂₂cycloalkyl, C₁-C₂₂ linear or branched fluoroalkyl, C₂-C₂₂ linear orbranched alkenyl, C₆-C₂₂ aryl, C₇-C₂₂ alkylenearyl, or mixtures thereof,R⁶ is C₁-C₃₀ linear or branched, substituted or unsubstituted alkylene;X is oxygen, sulfur, ═NR⁵, or mixtures thereof, u is 0 or 1.

When using one of the above L units, several embodiments of the presentinvention are especially useful to the formulator. For example, oneembodiment of the above linking units relates to the use of glycidylether linking units having a moiety of the general formula:

wherein B is a leaving group and the index w has a value such that thetotal number of continuous carbon atoms in the linking group is from 1to 30. Non-limiting examples of suitable leaving groups include halogen,tosyl, and the like. When the above glycidyl units are used to attach Runits, one embodiment of the present invention can have the formula:

Other ether linking groups include L units having the formula:—R⁶—O—R⁶—wherein one R⁶ unit is C₈-C₃₀ hydroxy substituted linear alkylene unitand one R⁶ unit is C₁-C₁₂ alkylene. A non-limiting example of thisembodiment includes an L unit having the formula:

wherein w is from 1 to 27 and R⁶ can comprise up to 30 continuous carbonatoms.

Another embodiment of the present invention relates to L units havingthe formula:

wherein R⁶ is substituted with one or more —COOR³⁰ units; a non-limitingexample of which has the formula:

wherein w is from 1 to 27.

R¹ units are units which provide the final anti-wrinkle compound withenhanced water dispesibility or enhanced water solubility. There are twotypes of R¹ units according to the present invention: nonionic andanionic units. The R¹ units have the formula:—[(CH₂)_(j)(R³O)_(k)]R⁴and can be divided into the following groups nonionic, anionic,zwitterionic, and cationic.

Nonionic Groups

R¹ units are nonionic units when R⁴ is hydrogen. For the nonionic aspectof the present invention each R¹ independently has the formula:—[(CH₂)_(j)(R³O)_(k)]Hwherein R³ is C₂-C₁₂ linear or branched alkylene, and mixtures thereof;the index j is from 0 to about 25; and the index k has an average valueof from 0 to about 50. One aspect of the present invention derives R¹units from polyalkylene glycols wherein the index j is 0 and in oneembodiment k has the average value of from about 3 to about 40.

In one embodiment R³ is C₂-C₆ linear or branched alkylene, while inanother embodiment each R³ unit is ethylene. In this latter case, theformulator may use or modify for use any number of existingpolyethyleneoxy oligomers or polymers, for example, polyethyleneglycolhaving an average molecular weight of 200 daltons (PEG200) k=5;polyethyleneglycol having an average molecular weight 400 daltons (PEG400) k=9, polyethyleneglycol having an average molecular weight of 1000daltons (PEG 1000) k=23.

The aspects of the present invention which comprise ethyleneoxy unitshave an index k with a value of from about 5 to about 30 or from about 5to about 20 depending upon the exact embodiment.

Another embodiment of the nonionic R¹ unit relates to the use ofpolyalkyleneoxy units wherein R³ is a mixture of alkylene units, forexample, block co-polymers of polyethylene glycol and polypropyleneglycol (EO/PO co-polymers, wherein said PO unit can be 1,2-propylene,1,3-propylene, or mixtures thereof), for example Pluronics® available exBASF. Another embodiment of these mixed block copolymers relates to R¹units which are each independently a mixture of C₂-C₄ linear or branchedalkylene.

However, it is not required for this aspect of the present inventionthat the index j is equal to 0. The formulator may attach an alkyleneunit to the backbone prior to attachment of the alkyleneoxy unit or thealkylene unit may be a part of the nonionic R¹ unit.

One aspect of the nonionic R¹ unit includes the formation of alkylethers, for example, units wherein the index k is equal to 0 and theindex j has a value of from 1 to about 12. Another embodiment of thisalkyl ether aspect includes methyl and ethyl ethers wherein j has thevalue 1 and 2 respectively.

The formulator may, for the purposes of adjusting the swellingproperties of the bulk material, admix differently modifiedpolysaccharides. For example, a portion of the material may be alkylether modified while another portion may be polyalkyleneoxy modified.This aspect of the present invention is described further herein below.

Anionic Groups

R¹ units are anionic units when R⁴ comprises a unit capable of having ananionic charge. For the purposes of the present invention any anionicunit is suitable for use as an R⁴ unit moiety if it provides therequired degree of dispersibility or water solubility necessary toachieve the anti-wrinkling benefits of the present invention.

One aspect of the present invention relates to R⁴ units selected fromthe group consisting of:

i) —CO₂M;

ii) —SO₂M;

iii) —SO₃M;

iv) —OSO₃M;

v) —PO₂M;

vi) —PO₃M;

vii) —OPO₃M; and

viii) mixtures thereof;

wherein M is hydrogen or a water soluble cation in a sufficient amountto provide charge neutrality. Non-limiting examples of M units aresodium, potassium, lithium, calcium, magnesium, ammonium, alkylammonium,and the like.

The formulator may also modify the anionic R⁴ units described herein.For example, sulfonation of a terminal alkylene can result in an anionicunit having the formula —CH₂(CHSO₃M)CH₂SO₃M, —CH₂(CHSO₂M)CH₂SO₃M, ormixtures thereof.

One embodiment of this aspect of the present invention relates to R¹units each independently having the formula:—(CH₂)_(j)CO₂Mnon-limiting examples of which include carboxymethyl, carboxyethyl, andthe like.

One aspect of the present invention relates to compounds having lessthan 50% of said units that are modified. The formula:

depicts an oligomer or polymer wherein x represents the number ofcellulosic units wherein all units are unsubstituted, y represents thenumber of cellulosic units wherein at least one hydrogen is replaced byan R unit, and z represents the number of cellulosic units wherein atleast one hydrogen is replaced by an R¹ unit. In the above example, xwill be about 50% or greater of the residues.

Another aspect of the present invention relates to cellulosic compoundswherein some residues are substituted by both an R and R¹ unit, whereinthe formulator can use the differential reactivity of the cellulosicunits, either because of their position in the chain, or because oftheir modified reactivity due to the first substitution, to have someresidues with two hydrogens replaced by an R or R¹ unit, for example,having the formula:

wherein x′ represents the number of cellulosic units having twohydrogens replaced by a R or R¹ unit, and x+x′=n

One aspect of the present invention relates to cellulosic compoundshaving the following ratios of substitution:

x y Z 50 25 25 70 15 15 80 10 10 85 10 5 90 5 5 95 3 2 97 1 2 x equalsnumber of residues having all hydroxyl units. y equals number ofresidues having one hydrogen replaced by an R unit. Z equals number ofresidues having one hydrogen replaced by an R¹ unit.Zwitterionic/Cationic Groups

Alternately, R¹ units are zwitterionic or cationic units when thepolysaccharide derivative comprises units capable of having cationiccharge alone or in conjunction with an anionic charge. For the purposesof the present invention, any cationic unit along with any anionic unitis suitable for use if it provides the required degree of dispersibilityor water solubility necessary to achieve the anti-wrinkling benefits ofthe present invention.

Formulations

One aspect of the present invention relates to compositions whichcomprise the modified polysaccharide oligomers or polymers. A firstembodiment relates to compositions which deliver through the washanti-wrinkle benefits. Formulations of this aspect can be modified foruse at any step in the laundry cycle, for example, as a pre-soak, as anaddition to surfactant comprising compositions, as a rinse-addedcomposition. Non-limiting examples of compositions which comprise thisaspect comprise:

-   -   a) from about 0.01% to about 99% by weight, of one or more        modified polysaccharides according to the present invention.        Another embodiment comprises from about 0.1% to about 50% by        weight of said modified polysaccharide, while yet another        embodiment comprises from about 0.5% to about 5% by weight, of        the anti-wrinkle component; and    -   b) the balance a suitable carrier.

Another embodiment of this aspect comprises in addition to a suitablecarrier other adjunct ingredients which can enhance the anti-wrinkleeffectiveness of the modified polysaccharides or which enhance thedelivery of said polysaccharides to fabric surface.

The compositions of the present invention further relate to the aspectof detersive surfactant comprising compositions, said compositionscomprising:

-   -   a) from about 0.01% to about 30% by weight, of one or more        modified polysaccharides according to the present invention.        Another embodiment comprises from about 0.1% to about 10% by        weight of said modified polysaccharide, while yet another        embodiment comprises from about 0.5% to about 5% by weight, of        the anti-wrinkle component;    -   b) from about 10% by weight, in one embodiment from about 10% to        about 80% by weight, in yet another embodiment from about 10% to        about 60%, wherein another embodiment comprises from about 15%        to about 30% by weight, of a surfactant system, said surfactant        system comprising:        -   i) from 0.01%, whereas depending upon which aspect or            embodiment of the present invention, the following ranges            are suitable: from about 0.1% to about 100%; from about 1%            to about 80%; from about 1% to about 60%, from about 1% to            about 30% by weight, of one or more anionic surfactants,            said anionic surfactants selected form the group consisting            of linear alkyl benzene sulphonates, mid-chain branched            alkyl benzene sulphonates; linear alkyl sulfates, mid-chain            branched sulfates, linear alkyleneoxy sulfates, mid-chain            branched alkyleneoxy sulfates; and mixtures thereof;        -   ii) optionally, from about 0.01%, whereas depending upon            which aspect or embodiment of the present invention, the            following ranges are suitable: from about 0.1% to about            100%; from about 1% to about 80%; from about 1% to about            60%, from about 1% to about 30% by weight, of one or more            nonionic surfactants selected from the group consisting of            alcohols, alcohol ethoxylates, polyoxyalkylene alkylamides,            and mixtures thereof; and    -   c) the balance carriers and other adjunct ingredients.

One embodiment of this aspect of the present invention relates tosurfactant systems comprising:

-   -   i) from about 0.01% by weight, of a surfactant selected from the        group consisting of alkyl sulfate surfactants, alkoxy sulfate        surfactants, mid-chain branched alkyl sulfate surfactants,        mid-chain branched alkoxy sulfate surfactants, mid-chain        branched aryl sulfonate surfactants, and mixtures thereof;    -   ii) from about 0.01% by weight, of one or more aryl sulphonate        anionic surfactants;    -   iii) from about 0.01% by weight, of one or more nonionic        surfactants.

A further embodiment relates to compositions comprising:

-   -   i) from about 0.01% by weight, of a surfactant selected from the        group consisting of alkyl sulfate surfactants, alkoxy sulfate        surfactants, and mixtures thereof;    -   ii) from about 0.01% by weight, of one or more nonionic        surfactants which are alkylethoxylates, alkyl alcohols, and        mixtures thereof.        Surfactants

As described hereinabove, one aspect of the present invention relates tocompositions comprising a surfactant system. The surfactant systems ofthe present invention may comprise any type of detersive surfactant,non-limiting examples of which include one or more mid-chain branchedalkyl sulfate surfactants, one or more mid-chain branched alkyl alkoxysulfate surfactants, one or more mid-chain branched aryl sulfonatesurfactants, one or more non mid-chain branched sulphonates, sulphates,cationic surfactants, zwitterionic surfactants, ampholytic surfactants,and mixtures thereof.

The total amount of surfactant present in the compositions of thepresent invention is from about 10% by weight, in one embodiment of thepresent invention the range of surfactant is from about 10% to about 80%by weight, of said composition. Another embodiment the amount ofsurfactant is from about 10% to about 60%, wherein another embodimentcomprises from about 15% to about 30% by weight, of said composition.

Nonlimiting examples of surfactants useful herein include:

-   a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);-   b) C₆-C₁₈ mid-chain branched aryl sulfonates (BLAS);-   c) C₁₀-C₂₀ primary, C₁₀-C₂₀-branched, and random alkyl sulfates    (AS);-   d) C₁₄-C₂₀ mid-chain branched alkyl sulfates (BAS);-   e) C₁₀-C₁₈ secondary (2,3) alkyl sulfates as described in U.S. Pat.    No. 3,234,258 Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041    Lutz, issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz et al.,    issued Sep. 20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issued    Feb. 14, 1995;-   f) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein preferably x is    from 1-7;-   g) C₁₄-C₂₀ mid-chain branched alkyl alkoxy sulfates (BAE_(x)S);-   h) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5    ethoxy units;-   i) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylates    wherein the alkoxylate units are a mixture of ethyleneoxy and    propyleneoxy units, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol    condensates with ethylene oxide/propylene oxide block polymers inter    alia Pluronic® ex BASF which are disclosed in U.S. Pat. No.    3,929,678 Laughlin et al., issued Dec. 30, 1975;-   j) C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAE_(x);-   k) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647    Llenado, issued Jan. 26, 1986;-   l) Pseudoquat surfactants having the formula:    wherein R is C₄-C₁₀ alkyl, R¹ is selected from the group consisting    of C₁-C₄ alkyl, —(CH₂CHR²O)_(y)H, and mixtures thereof; R² is    hydrogen, ethyl, methyl, and mixtures thereof; y is from 1 to 5; x    is from 2 to 4; for the purposes of the present invention, a    particularly useful pseudoquat surfactant comprises R equal to an    admixture of C₈-C₁₀ alkyl, R¹ is equal to methyl; and x equal to 3;    these surfactants are described in U.S. Pat. No. 5,916,862 Morelli    et al., issued Jun. 29, 1999;-   m) Polyhydroxy fatty acid amides having the formula:    wherein R⁷ is C₅-C₃₁ alkyl; R⁸ is selected from the group consisting    of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, Q is a    polyhydroxyalkyl moiety having a linear alkyl chain with at least 3    hydroxyls directly connected to the chain, or an alkoxylated    derivative thereof; preferred alkoxy is ethoxy or propoxy, and    mixtures thereof. These surfactants are described in U.S. Pat. No.    5,489,393 Connor et al., issued Feb. 6, 1996; and U.S. Pat. No.    5,45,982 Murch et al., issued Oct. 3, 1995.

The mid-chain branched alkyl sulfate surfactants of the presentinvention have the formula:

the alkyl alkoxy sulfates have the formula:

the alkyl alkoxylates have the formula:

wherein R, R¹, and R² are each independently hydrogen, C₁-C₃ alkyl, andmixtures thereof; provided at least one of R, R¹, and R² is nothydrogen; preferably R, R¹, and R² are methyl; preferably one of R, R¹,and R² is methyl and the other units are hydrogen. The total number ofcarbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxysulfate surfactants is from 14 to 20; the index w is an integer from 0to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z isan integer of at least 1; provided w+x+y+z is from 8 to 14 and the totalnumber of carbon atoms in a surfactant is from 14 to 20; R³ is C₁-C₄linear or branched alkylene, preferably ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.

M denotes a cation, preferably hydrogen, a water soluble cation, andmixtures thereof. Non-limiting examples of water soluble cations includesodium, potassium, lithium, ammonium, alkyl ammonium, and mixturesthereof.

Adjunct Ingredients

The following are non-limiting examples of adjunct ingredients useful inthe laundry compositions of the present invention, said adjunctingredients include builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.

Builders

The laundry detergent compositions of the present invention preferablycomprise one or more detergent builders or builder systems. Whenpresent, the compositions will typically comprise at least about 1%builder, another embodiment comprises from 5% to about 80% by weight ofa builder. Other embodiments comprise from about 10% to about 30% byweight, of detergent builder preferably to about 50%, more preferably.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. Examples of silicate-builders are thealkali metal silicates, examples of which include those having aSiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1 and layered silicates asdescribed in U.S. Pat. No. 4,664,839 Rieck, issued May 12, 1987 whichinclude NaSKS-6® ex Hoechst. Others include NaSKS-5®, NaSKS-7®, andNaSKS-11® also ex Hoechst.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders include those having the empirical formula:[M_(z)(zAlO₂)_(y)]xH₂Owherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264, known as Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.In one embodiment, the crystalline aluminosilicate ion exchange materialhas the formula:Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]xH₂Owherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Preferably, the aluminosilicate has aparticle size of about 0.1-10 microns in diameter.

Included among the polycarboxylate builders are those disclosed in U.S.Pat. No. 3,128,287 Berg, issued Apr. 7, 1964, and U.S. Pat. No.3,635,830 Lamberti et al., issued Jan. 18, 1972; U.S. Pat. No. 4,663,071Bush et al., issued May 5, 1987; U.S. Pat. No. 3,923,679 Rapko, issuedDec. 2, 1975; U.S. Pat. No. 4,158,635 Crutchfield et al., issued Jun.19, 1979; U.S. Pat. No. 4,120,874 Crutchfield et al., issued Oct. 17,1978; and U.S. Pat. No. 4,102,903 Crutchfield et al., issued Jul. 25,1978.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Other suitable builders are disclosed in U.S. Pat. No. 4,566,984, Bush,issued Jan. 28, 1986; U.S. Pat. No. 4,144,226, Crutchfield et al.,issued Mar. 13, 1979 and in U.S. Pat. No. 3,308,067, Diehl, issued Mar.7, 1967 and U.S. Pat. No. 3,723,322.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders. In embodiments wherein phosphorus-based builders areused the various alkali metal phosphates, inter alia, sodiumtripolyphosphates, sodium pyrophosphate and sodium orthophosphate can beused. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonateand other known phosphonates as described in U.S. Pat. Nos. 3,159,581;3,213,030; 3,422,021; 3,400,148 and 3,422,137.

Dispersants

The compositions of the present invention may comprise from about 0.01%to about 10% by weight of one or more polyalkyleneimine dispersants asdescribed in U.S. Pat. No. 4,597,898 Vander Meer, issued Jul. 1, 1986;European Patent Application 111,965 Oh and Gosselink, published Jun. 27,1984; European Patent Application 111,984 Gosselink, published Jun. 27,1984; European Patent Application 112,592 Gosselink, published Jul. 4,1984; U.S. Pat. No. 4,548,744 Connor, issued Oct. 22, 1985; and U.S.Pat. No. 5,565,145 Watson et al., issued Oct. 15, 1996. However, anysuitable clay/soil dispersant or anti-redepostion agent can be used inthe laundry compositions of the present invention.

The compositions of the present invention may comprise from about 0.01%to about 10% by weight, of one or more polymeric polycarboxylates andpolyethylene glycols, for example, those derived from acrylic acid,maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconiticacid, mesaconic acid, citraconic acid and methylenemalonic acid. Thesemonomers can be used alone, in combination with each other monomers orin combination of units such as vinylmethyl ether, styrene, ethylene,etc. provided that such segments do not constitute more than about 40%by weight, of said polymer.

One embodiment comprises from about 0.01% to about 10% by weight,polymeric polycarboxylates derived from acrylic acid having an averagemolecular weight of from about 2,000 to 10,000, or in another embodimentfrom about 4,000 to 7,000 or from about 4,000 to 5,000. Polyacrylates ofthis type are disclosed in U.S. Pat. No. 3,308,067 Diehl, issued Mar. 7,1967. In addition, acrylic/maleic-based copolymers having averagemolecular weights ranging from about 2,000 to 100,000 are useful.However, depending upon the embodiment, molecular weight ranges mayinclude from about 5,000 to 75,000, and from about 7,000, to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, however, about 10:1 to 2:1 is alsouseful as a further embodiment. Acrylate/maleate copolymers described inEuropean Patent Application No. 66915, published Dec. 15, 1982, and EP193,360, published Sep. 3, 1986.

A further embodiment comprises from about 0.01% to about 10% by weight,of polyethylene glycol (PEG) having molecular weight ranges offrom about500 to about 100,000; from about 1,000 to about 50,000; and from about1,500 to about 10,000.

Soil Release Agents

The compositions according to the present invention may optionallycomprise one or more soil release agents. If utilized, soil releaseagents will generally comprise from about 0.01% to about 10% by weightof the composition, however, one embodiment comprises from about 0.1% toabout 5% by weight of said composition, whereas other embodimentscomprise from about 0.2% to about 3% by weight, of the composition.

Polymers suitable for use in the present invention are described in U.S.Pat. No. 5,843,878 Gosselink et al., issued Dec. 1, 199; U.S. Pat. No.5,834,412 Rohrbaugh et al., issued Nov. 10, 1998; U.S. Pat. No.5,728,671 Rohrbaugh et al., issued Mar. 17, 1998; U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al., issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,771,730 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No. 711,730Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580 Gosselinkissued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al., issued Dec.28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25, 1976; U.S. Pat.No. 3,893,929 Basadur, issued Jul. 8, 1975; and European PatentApplication 0 219 048, published Apr. 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al; U.S. Pat. No. 4,579,681 Ruppert et al.;U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A, 1988 toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 toUnilever N.V., 1974.

Method of Use

The present invention further relates to a method for providinganti-wrinkle benefits to fabric, preferably clothing, said methodcomprising the step of contacting fabric in need of cleaning with anaqueous solution of a laundry detergent composition comprising:

-   -   a) from about 0.01% to about 30% by weight, of the anti-wrinkle        component.    -   b) from about 10% by weight, of a surfactant system, said        surfactant system comprising:        -   i) from about 0.01% by weight, of one or more anionic            surfactants, said anionic surfactants selected form the            group consisting of linear alkyl benzene sulphonates,            mid-chain branched alkyl benzene sulphonates; linear alkyl            sulfates, mid-chain branched sulfates, linear alkyleneoxy            sulfates, mid-chain branched alkyleneoxy sulfates; and            mixtures thereof; and        -   ii) optionally, from about 0.01% by weight, of one or more            nonionic surfactants selected from the group consisting of            alcohols, alcohol ethoxylates, polyoxyalkylene alkylamides,            and mixtures thereof; and    -   c) the balance carriers and other adjunct ingredients.

The compositions of the present invention can be suitably prepared byany process chosen by the formulator, non-limiting examples of which aredescribed in U.S. Pat. No. 5,691,297 Nassano et al., issued Nov. 11,1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12, 1996; U.S.Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996; U.S. Pat. No.5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S. Pat. No.5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No. 5,489,392Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303 Capeci etal., issued Jan. 23, 1996 all of which are incorporated herein byreference.

EXAMPLES

The following are non-limiting examples of procedures for preparing thesilicon comprising modified polysaccharides of the present invention.

Example 1

To a 3 L flask is charged finely ground birch cellulose (60 g), ethanol(420 mL), isopropanol (420 mL) and water (42 mL). The solution isstirred for 30 minutes after which time NaOH (12 g of a 50% w/wsolution) is added over 5 minutes. After stirring an additional 30minutes, (3-glycidoxypropyl) pentamethylsiloxane (2.4 g) is added over 5minutes after which the reaction is heated to 70° C. for two hours. Theflask is cooled to room temperature and NaOH (31 g of a 50% w/wsolution) is added over 5 minutes. Once the reaction has stirred anadditional 30 minutes monochloroacetic acid (30 g of an 80% aqueoussolution) is added slowly and the resulting solution heated to 70° C.for 1 hour. After cooling, the solids are removed by filtration, washedwith ethanol (500 mL) and dried under vacuum to yield the desiredmodified cellulose.

Example 2

To a 3 L flask is charged finely ground birch cellulose (50 g), ethanol(350 mL), isopropanol (350 mL) and water (35 mL). The solution isstirred for 30 minutes after which time NaOH (48.5 g of a 50% w/wsolution) is added over 5 minutes. After stirring an additional 30minutes, monochloro acetic acid (25 g of an 80% aqueous solution) and3-chloropropyltrimethylsilane (5 g) is added over 5 minutes after whichthe reaction is heated to 70° C. for two hours. After cooling, thesolids are removed by filtration, washed with ethanol (500 mL) and driedunder vacuum to yield the desired modified cellulose.

Example 3

To a 2 L flask is charged potato starch (45 g) and methanol (75 mL). Thesolution is stirred for 10 minutes after which time NaOH (26.5 g of a50% w/w solution) is added over 5 minutes. After stirring an additional2 hrs, (3-glycidoxypropyl) pentamethylsiloxane (2.4 g) is added over 5minutes after which the reaction is heated to 60° C. for three hours.Next, monochloroacetic acid (19 g of an 80% aqueous solution) is addedslowly and the resulting solution heated at 60° C. for 3 hours. Aftercooling, the reaction was slurried in 200 ml isopropanol and the solidsare removed by filtration, washed with methanol (200 mL) and dried undervacuum to yield the desired modified starch.

Example 4

To a 3 L flask is charged guar flour (45 g), isopropanol (100 mL) andwater (30 mL). The solution is stirred for 30 minutes after which timeNaOH (30 g of a 50% w/w solution) is added over 5 minutes. Afterstirring an additional 30 minutes, monochloro acetic acid (19 g of an80% aqueous solution) and 3-chloropropyltrimethylsilane (5 g) is addedover 5 minutes after which the reaction is heated to 70° C. for twohours. After cooling, the solids are removed by filtration, washed withethanol (500 mL) and dried under vacuum to yield the desired modifiedguar.

The following are non-limiting examples of compositions according to thepresent invention.

TABLE I weight % Ingredients 5 6 7 8 Polyhydroxy coco-fatty acid amide2.50 4.00 4.50 — NEODOL 24-7¹ — 4.50 — — NEODOL 23-9² 0.63 — 4.50 2.00C₁₂-C₁₅ Alkyl ethoxylate sulphate 20.15 4.00 5.50 20.50 C₁₂-C₁₅ Alkylsulfate — 14.00 15.00 — C11.8 linear alkylbenzene — — — 6.00 sulfonateC₈-C₁₀-Amidopropyl Amine — 1.30 — — C₁₀-Amidopropyl Amine 0.50 — — 1.50Citric acid 3.00 2.00 3.00 2.50 C₁₂-C₁₈ fatty acid 2.00 6.50 5.00 5.00Rapeseed fatty acid — 4.10 — 6.50 Ethanol 3.36 1.53 5.60 0.50Propanediol 7.40 9.20 6.22 4.00 Monoethanolamine 1.00 7.90 8.68 0.50Sodium hydroxide 2.75 1.30 0.75 4.40 Sodium p-toluene sulfonate 2.25 —1.90 — Borax/Boric acid 2.50 2.00 3.50 2.50 Protease³ 0.88 0.74 1.500.88 Lipolase⁴ — 0.12 0.18 — Duramyl⁵ 0.15 0.11 — 0.15 CAREZYME 0.0530.028 0.080 0.053 Dispersant⁶ 0.60 0.70 1.50 0.60 Ethoxylatedpolyalkyleneimine⁷ 1.20 0.70 1.50 1.20 Optical Brightener 0.13 0.15 0.300.15 Polyamine⁸ 5.00 1.00 — — Polyamine⁹ — — 0.25 0.50 Anti-wrinkleagent¹⁰ Suds suppresser 0.12 0.28 0.12 0.12 Minors, aesthetics,stabilizers, balance balance balance balance water ¹C₁₂-C₁₄ alkylethoxylate as sold by Shell Oil Co. ²C₁₂-C₁₃ alkyl ethoxylate as sold byShell Oil Co. ³Protease B variant of BPN′ wherein Tyr 17 is replacedwith Leu. ⁴Derived from Humicola lanuginosa and commercially availablefrom Novo. ⁵Disclosed in WO 9510603 A and available from Novo.⁶Hydrophilic dispersant PEI 189 E₁₅-E₁₈ according to U.S. Pat. No.4,597,898, Vander Meer, issued Jul. 1, 1986. ⁷Polyalkyleneiminedispersant PEI 600 E₂₀. ⁸Lupasol ® SK ex BASF. ⁹Lupasol ® SKA ex BASF.¹⁰According to Example 1.

TABLE II weight % Ingredients 9 10 11 Anionic surfactant¹ 28.69  28.99 34.80  Nonionic surfactant² 5.93 5.93 — Cationic surfactant³ — — 5.51Bleach activator system⁴ 6.10 6.10 4.53 Photobleach⁵ 0.03 0.03 0.03 Sudssupressor⁶ 3.46 3.46 1.89 Builder⁷ 6.75 6.75 — Builder⁸ 14.67  14.67 10.68  Dye transfer inhibitor⁹ 0.14 0.14 — Perfume¹⁰ 0.25 0.25 — C₁₂-C₁₅alkyl ethoxy (7.0) alcohol¹¹ spray on 5.82 5.82 — PEG 200¹² — 1.2  —Zwitterionic hexamethylene diamine¹³ 1.50 1.25 1.08 Optical brightener0.28 0.28  0.183 Sodium carbonate 5.02 5.02 13.96  Sodium perborate17.80  17.80  — Sodium percarbonate — — 14.33  Sodium HEDP 0.85 0.85 —Anti-wrinkle agent Perfume 0.35 0.35 0.46 Protease enzyme 0.92 0.92 0.89Cellulase enzyme 0.27 0.27 0.21 Lipase enzyme 0.23 0.23  0.275 Amylaseenzyme 0.75 0.75 1.04 Citric acid — — 7.16 Soil release polymer¹⁴ 0.500.50 0.50 Minors¹⁵ balance balance balance ¹Anionic surfactantagglomeration comprising 38% surfactant, 22% zeolite, 40% sodiumcarbonate. ²Nonionic surfactant agglomeration comprising 26% surfactant,48% zeolite, 26% sodium carbonate. ³Cationic surfactant agglomerationcomprising 24% surfactant, 64% zeolite, 12% sodium sulphate. ⁴Bleachactivator system comprising 81% TAED, 17% acrylic/maleic copolymer (acidform), 2% moisture. ⁵Encapsulated zinc phthalocyanine (10%) according toU.S. Pat. No. 4,033,718, Holcombe et al., issued Jul. 5, 1977. ⁶Zeolite.⁷Admixture comprising 11.5% silicone oil ex Dow Corning and 88.5%starch. ⁸Layered silicate comprising 78% SKS-6 ex Hoechst and 22% citricacid. ⁹Dye transfer inhibitor agglomerate comprises 21% PVNO/PVPVI, 61%zeolite and 18% sodium carbonate. ¹⁰Perfume encapsulate comprises 50%perfume and 50% starch. ¹¹C₁₂-C₁₅ alkyl ethoxy (7.0) alcohol and 17% byweight, of polyethylene glycol having an average molecular weight ofabout 4000. ¹²Polyethylene glycol having an average molecular weight of200. ¹³According to Example 1. ¹⁴Soil release polymer according to U.S.Pat. No. 5,415,807 Gosselink et al., issued May 16, 1995. ¹⁵Balance to100% can, for example, include minors like, processing aids, additionalwater, and fillers, including CaCO₃, talc, silicates, etc.

1. A compound having the formula:

wherein each R unit is independently a siloxane unit having the formula:

wherein each R² is independently a C₁-C₂₂ linear or branched,substituted or unsubstituted hydrocarbyl moiety; the index p is from 0to about 50; L is a linking group; the index q is 0 or 1; each R¹ unitis independently a fabric substantive unit having the formula:—[(CH₂)_(j)(R³O)_(k)]R⁴ wherein R³ is C₂-C₁₂ linear or branchedalkylene; R⁴ is hydrogen, an anionic unit, and mixtures thereof; theindex j is from 0 to about 25; the index k is from 0 to about 50; thesum of the indices x+y+z=n wherein n has an average value of from 5 toabout
 6000. 2. The compound of claim 1 wherein each R² is independentlyphenyl, C₁-C₁₈ alkyl, or mixtures thereof.
 3. The compound of claim 2wherein each R² is independently C₁-C₁₂ alkyl, or mixtures thereof. 4.The compound of claim 3 wherein each R² is independently C₁-C₆ alkyl, ormixtures thereof.
 5. The compound of claim 1 wherein the index p is from0 to about
 20. 6. The compound of claim 5 wherein the index p is from 0to about
 10. 7. The compound of claim 1 wherein L is a linking groupselected from the group consisting of: i) —[C(R⁵)₂]_(d)—; wherein d isfrom 1 to 30; ii) —[C(R⁵)₂]_(d)(CH═CH)_(d′)—; wherein d is from 0 to 30;d′ is from 1 to 30; iii) —C(X)—; iv) —OC(X)—; v) —C(X)O—; vi)—[C(R⁵)₂]_(e)C(X)X(R⁶O)_(d)—; wherein d is from 0 to 30; e is from 1 to30; vii) —(OR⁶)_(j)XC(X)[C(R⁵)₂]_(e)—; wherein d is from 0 to 30; e isfrom 1 to 30; viii) —[C(R⁵)₂]_(e)C(X)(R⁶O)_(j)—; wherein d is from 0 to30; e is from 1 to 30; ix) —(OR⁶)_(d)C(X)[C(R⁵)₂]_(e)—; wherein d isfrom 0 to 30; e is from 1 to 30; x) —C(X)NR⁵—; xi) —C(X)R⁶C(X)—; xii)—C(X)NR⁵C(X)—; xiii) —C(X)NR⁵R⁶NR⁵C(X)—; xiv) —NR⁵C(X)—; xv)—NR⁵C(X)NR⁵—; xvi) —NR⁵C(X)R⁶NR⁵—; xvii) —NR⁵R⁶C(X)NR⁵—; xviii)—NR⁵C(X)R⁶C(X)O—; xix) —OC(X)R⁶C(X)NR⁵—; xx) —NR⁵C(X)R⁶C(X)O—; xxi)—NR⁵C(X)NR⁵R⁶—; xxii) —R⁶NR⁵C(X)NR⁵—; xxiii) —NR⁵C(X)NR⁵R⁶—; xxiv)—R⁶NR⁵C(X)NR⁵R⁶—; xxv) —NR⁵—; xxvi) —R⁶NR⁵—; xxvii) —NR⁵R⁶—; xxviii)—NR⁵N═N—; xxix) —NR⁵NR⁵— xxx) —OR⁶—; xxxi) —R⁶O—; xxxii) —R⁶OR⁶—;xxxiii) —(R⁶)_(u)C(X)(R⁶)_(u)—; xxxiv) —(R⁶)_(u)OC(O)(R⁶)_(u)—; xxxv)—(R⁶)_(u)C(O)O(R⁶)_(u)—; and xxxvi) —(R⁶)_(u)OC(O)O(R⁶)_(u)—; wherein R⁵is hydrogen, C₁-C₂₂ linear or branched alkyl, C₁-C₂₂ cycloalkyl, C₁-C₂₂linear or branched fluoroalkyl, C₂-C₂₂ linear or branched alkenyl,C₆-C₂₂ aryl, C₇-C₂₂ alkylenearyl, or mixtures thereof; R⁶ is C₁-C₃₀linear or branched, substituted or unsubstituted alkylene; X is oxygen,sulfur, ═NR⁵, or mixtures thereof; and u is 0 or
 1. 8. The compound ofclaim 7 wherein the unit which substitutes the alkylene unit is selectedfrom the group consisting of: i) —NHCOR³⁰; ii) —COR³⁰; iii) —COOR³⁰; iv)—COCH═CH₂; v) —C(═NH)NH₂; vi) —N(R³⁰)₂; vii) —NHC₆H₅; viii) ═CHC₆H₅; ix)—CON(R³⁰)₂; x) —CONHNH₂; xi) —NHCN; xii) —OCN; xiii) —CN; xiv) F, Cl,Br, I, and mixtures thereof; xv) ═O; xvi) —OR³⁰; xvii) —NHCHO; xviii)—OH; xix) —NHN(R³⁰)₂; xx) ═NR³⁰; xxi) ═NOR³⁰; xxii) —NHOR³⁰; xxiii)—CNO; xxiv) —NCS; xxv) ═C(R³⁰)₂; xxvi) —SO₃M; xxvii) —OSO₃M; xxviii)—SCN; xxix) —P(O)H₂; xxx) —PO₂; xxxi) —P(O)(OH)₂; xxxii) —SO₂NH₂;xxxiii) —SO₂R³⁰; xxxiv) —NO₂; xxxv) trihalomethyl having the formula:—CF₃, —CCl₃, —CBr₃; xxxvi) and mixtures thereof; wherein R³⁰ ishydrogen, C₁-C₂₀ linear or branched alkyl, C₆-C₂₀ aryl, C₇-C₂₀alkylenearyl, or mixtures thereof; M is hydrogen, or a salt formingcation.
 9. The compound of claim 7 wherein L has the formula:—R⁶—O—R⁶— wherein one R⁶ unit is C₈-C₃₀ hydroxy substituted linearalkylene unit and one R⁶ unit is C₁-C₁₂ alkylene.
 10. The compound ofclaim 9 wherein L is a glycidyl ether unit having the formula:

wherein w is from 1 to
 27. 11. The compound of claim 7 wherein L is aglycidyl ether unit having the formula:

wherein w is from 1 to
 27. 12. The compound of claim 7 wherein L has theformula:

wherein R⁶ is substituted with one or more —COOR³⁰ units.
 13. Thecompound of claim 12 wherein L has the formula:

w is from 1 to
 27. 14. The compound of claim 1 wherein R³ is C₂-C₆linear or branched alkylene; R⁴ is hydrogen; j is 0; and k is from 3 to50.
 15. The compound of claim 14 wherein R³ is a C₂-C₄ linear orbranched alkylene.
 16. The compound of claim 15 wherein k is from 5 to30.
 17. The compound of claim 16 wherein k is from 5 to
 20. 18. Thecompound of claim 1 wherein R⁴ is an anionic unit selected from thegroup consisting of: i) —CO₂M; ii) —SO₂M; iii) —SO₃M; iv) —OSO₃M; v)—PO₂M; vi) —PO₃M; vii) —OPO₃M; viii) and mixtures thereof; wherein M ishydrogen or a water soluble cation in a sufficient amount to providecharge neutrality.
 19. The compound of claim 1 wherein n has an averagevalue of from about 10 to about
 3000. 20. The compound of claim 19wherein n has an average value of from about 15 to about
 1000. 21. Acomposition providing anti-wrinkle benefits to fabric, the compositioncomprising: a) from about 0.01% to about 99% by weight, of ananti-wrinkle agent having the formula:

wherein each R unit is independently a siloxane unit having the formula:

wherein each R² is independently a C₁-C₂₂ linear or branched,substituted or unsubstituted hydrocarbyl moiety; the index p is from 0to about 50; L is a linking group; the index q is 0 or 1; and each R¹unit is independently a fabric substantive unit having the formula:—[(CH₂)_(j)(R³O)_(k)]R⁴ wherein R³ is C₂-C₁₂ linear or branchedalkylene; R⁴ is hydrogen, an anionic unit, or mixtures thereof; theindex j is from 0 to about 25; the index k is from 0 to about 50; andthe sum of the indices x+y+z=n wherein n has an average value of from 5to about 6000; and b) the balance carriers.
 22. A laundry detergentcomposition comprising: a) from about 0.01% to about 30% by weight, ofan anti-wrinkle agent having the formula:

wherein each R unit is independently a siloxane unit having the formula:

wherein each R² is independently a C₁-C₂₂ linear or branched,substituted or unsubstituted hydrocarbyl moiety; the index p is from 0to about 50; L is a linking group; the index q is 0 or 1; and each R¹unit is independently a fabric substantive unit having the formula:—[(CH₂)_(j)(R³O)_(k)]R⁴ wherein each R³ is independently C₂-C₁₂ linearor branched alkylene; R⁴ is hydrogen, an anionic unit, and mixturesthereof; the index j is from 0 to about 25; the index k is from 0 toabout 50; and the sum of the indices x+y+z=n wherein n has an averagevalue of from 5 to about 6000; b) from about 10% to about 80% by weight,of a surfactant system; and c) the balance carriers and other adjunctingredients.
 23. The composition of claim 22 wherein the surfactantsystem comprises: i) from about 0.01% by weight, of a surfactantselected from the group consisting of alkyl sulfate surfactants, alkoxysulfate surfactants, mid-chain branched alkyl sulfate surfactants,mid-chain branched alkoxy sulfate surfactants, mid-chain branched arylsulfonate surfactants, and mixtures thereof; ii) from about 0.01% byweight, of one or more aryl sulphonate anionic surfactants; iii) fromabout 0.01% by weight, of one or more nonionic surfactants.